EP0696580B1 - Amines tertiaires ayant des groupes d'uréthane et carbonate et leur application comme catalyseurs dans la préparation des polyuréthanes - Google Patents

Amines tertiaires ayant des groupes d'uréthane et carbonate et leur application comme catalyseurs dans la préparation des polyuréthanes Download PDF

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Publication number
EP0696580B1
EP0696580B1 EP95111812A EP95111812A EP0696580B1 EP 0696580 B1 EP0696580 B1 EP 0696580B1 EP 95111812 A EP95111812 A EP 95111812A EP 95111812 A EP95111812 A EP 95111812A EP 0696580 B1 EP0696580 B1 EP 0696580B1
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EP
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Prior art keywords
groups
carbonate
carbonic acid
hydroxyl groups
amines
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP95111812A
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German (de)
English (en)
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EP0696580A2 (fr
EP0696580A3 (fr
Inventor
Klaus Dr. König
Ulrich Dr. Liman
Josef Dr. Sanders
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Bayer AG
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Bayer AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/03—Monoamines
    • C07C211/05—Mono-, di- or tri-ethylamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1841—Catalysts containing secondary or tertiary amines or salts thereof having carbonyl groups which may be linked to one or more nitrogen or oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products

Definitions

  • the invention relates to a process for the production of new, carbonate and Urethane groups and optionally tertiary hydroxyl groups Amines, the compounds obtainable by this process and their Use as catalysts in the production of polyurethane plastics, in particular in the production of composite bodies by back-foaming Plastic films with a reaction mixture that reacts to form polyurethane foam.
  • DE-OS 40 30 515 describes the production of tert. Amino groups containing urethanes by reacting cyclic carbonates such as e.g. Ethylene or propylene carbonate and both primary and tertiary amino groups having amines, and their use as catalysts for Manufacture of polyurethanes.
  • the resulting urethanes are catalytically active and have hydroxyl groups capable of incorporation into the polyurethane matrix.
  • the invention also relates to those obtainable by this process Carbonate and urethane groups and optionally hydroxyl groups tertiary amines, and their use as catalysts in the manufacture of polyurethane plastics by the isocyanate polyaddition process, in particular in the production of composite bodies by back-foaming Plastic films with a reaction mixture that reacts to form polyurethane foam.
  • Starting materials for the process according to the invention are a) two or trihydric alcohols of the type described in more detail below, b) primary tertiary Diamines of the type described below and c) carbonic acid derivatives Art described below.
  • the alcohol component a) consists of at least one alcohol of the above general formula (I) mentioned.
  • Alcohol component a) for example (i) optionally aliphatic diols containing ether groups Molecular weight range 90 to 400, preferably 106 to 250, (ii) optionally Aliphatic triols of the molecular weight range containing ether groups 120 to 400, preferably 134 to 400 and (iii) any mixtures of two and trihydric alcohols (i) and (ii).
  • suitable dihydric alcohols (i) are 1,4-butanediol, 1,5-pentanediol, 3-methyl-pentanediol-1,5, 2,2,4-trimethylhexanediol-1.6, the isomers Heptanediols, octanediols, nonanediols or decanediols, and those per se known addition products of the mentioned molecular weight range of Ethylene oxide and / or propylene oxide on such alcohols or on ethylene glycol or propylene glycol.
  • Propylene oxide content the hydrophilicity or the solubility of the end products in Water or polyether polyol can be affected.
  • Suitable trihydric alcohols (ii) are, for example, trimethylolethane, trimethylolpropane, as well as the known addition products of the above Molecular weight range of ethylene oxide and / or propylene oxide to such Triols, here too the hydrophilicity via the ethylene or propylene oxide component or solubility of the end products in water or polyether polyol can be.
  • the preferred polyhydric alcohol (ii) is trimethylolpropane.
  • the primary tertiary amines b) are those of the general formula (II) already mentioned above, preference being given in particular to those for which A represents an alkylene radical having 2 to 4 carbon atoms and R 1 and R 2 each represent methyl groups stand.
  • the primary tertiary diamines can be prepared, for example, by Alkylation of mono-protected diprimeric amines, e.g. Aminoalkyl phthalimides, and subsequent hydrolysis or hydrazinolysis or, preferably, by Addition of aziridine or acrylonitrile to secondary amines such as e.g. Dimethylamine, diethylamine, dipropylamine, piperidine or morpholine and subsequent hydrogenation of the cyanoethylated amines.
  • mono-protected diprimeric amines e.g. Aminoalkyl phthalimides
  • hydrolysis or hydrazinolysis e.g.
  • aziridine or acrylonitrile e.g. Dimethylamine, diethylamine, dipropylamine, piperidine or morpholine and subsequent hydrogenation of the cyanoethylated amines.
  • Suitable amines b) are: 1- (dimethylamino) -3-aminopropane, 1- (diethylamino) -3-aminopropane, 1- (di-n-propylamino-3-aminopropane, 1- (dimethylamino) -2-methyl-3-aminopropane, 1- (dimethylamino) -4-aminobutane, 1- (dimethylamino) -5-aminopentane, N- (2-aminoethyl) morpholine, N- (3-aminopropyl) morpholine, N- (2-aminoethyl) piperidine or N- (3-aminopropyl) piperidine. It is also possible, To use mixtures of the listed amines. 1- (Dimethylamino) -3-aminopropane is preferred.
  • the carbonic acid derivatives c) are compounds with Alcohols with carbonate formation, or with alcohols and primary amines under React urethane formation, selected from the group consisting of optionally cyclic carbonates of the above general formula (III), Urea, phosgene and bischlorocarbonate of alcohols of the above mentioned general formula (I), the used as component a) polyhydric alcohols on the one hand and those in the form of bischlorocarbonic acid esters alcohols of the formula (I) used, on the other hand, in each case those made above Definition of Q and n correspond, but do not have to be identical.
  • Prefers are optionally cyclic in the process according to the invention Carbonates of the general formula (III) mentioned above are used. Examples suitable carbonates are dimethyl, diethyl, di-n-propyl, di-n-butyl, Diphenyl, ethylene and propylene carbonate. Diphenyl carbonate is particularly preferred used.
  • the method according to the invention can be carried out in one or two stages.
  • the polyhydroxyl compounds a) and Carbonates c) optionally after melting at about 50 to 80 ° C, homogenized before the amine component b) is metered in with stirring.
  • the internal temperature is gradually increased to a maximum of 200 ° C and leave there until the distillation is finished.
  • Last traces more fleeting Components can be created by applying high vacuum or by Azeotropic distillation with the addition of tractors such as Water or Ethylene glycol can be removed.
  • the reaction is preferably carried out without a solvent, but the In some cases the use of solvents is expedient or necessary be, e.g. when using poorly soluble starting materials. In such cases come Solvents into consideration which do not react with the reaction components and have a boiling point that is below the boiling point of the Hydroxyl component of the carbonate used is a perfect one to allow separation by distillation.
  • hydrocarbons are suitable such as toluene or xylene, halogenated hydrocarbons such as Chlorobenzene or dichlorobenzene, ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Diphenyl ether or dioxane and amides such as dimethylformamide, Dimethylacetamide or N-methylpyrrolidone.
  • ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Diphenyl ether or dioxane
  • amides such as dimethylformamide, Dimethylacetamide or N-methylpyrrolidone.
  • catalysts such as alkali bases or transition metal compounds such as.
  • Dibutyltin oxide, or tetrabutyltitanate may be beneficial, however, is one Operation without addition of catalyst preferred.
  • the first stage is carried out in a manner known per se from polyol component a) and carbonic acid derivative c) according to known processes, preferably while maintaining a molar ratio of hydroxyl groups of component a) to carbonic acid derivatives c) of 2: 1 to 3: 1, a polycarbonate is produced, which is then reacted with amines b) in the sense of an aminolysis reaction of the carbonate groups.
  • the polycarbonate intermediates obtained are then reacted with amine components b).
  • the amount of amine component is measured so that 0.2 to 0.5 mol of amine component b) is used per mole of carbonate group.
  • the reaction can be carried out, for example, by initially introducing the optionally melted polycarbonate at room temperature or at an elevated temperature of about 60 to 80 ° C. and adding the amine component b) with stirring. The mixture is then stirred at 80 to 120 ° C until the primary amino groups of the amine component have reacted. This can be determined, for example, by titration with HCl or perchloric acid.
  • the second stage of this variant of the method according to the invention is preferred carried out without solvent, however the use of Solvents may be appropriate in some cases, e.g. at Use of poorly soluble starting materials. In such cases, solvents come into consideration, which do not react with the reaction components. Suitable are e.g. the solvents listed above.
  • the compounds of the invention which have tertiary amino groups are largely odorless.
  • the starting materials in particular of the hydroxyl compounds a) products are obtained which are excellent Compatibility with the polyether polyols common in polyurethane chemistry exhibit. They can therefore advantageously be used as catalysts or Activators for the production of polyurethanes, in particular polyurethane foams from the usual starting materials are used.
  • the compounds according to the invention generally in amounts of 1 to 20 wt .-%, based on the entire reaction mixture reacting to form polyurethane foam.
  • the compounds according to the invention are merely to auxiliaries, in addition to the usual polyhydroxyl compounds, in particular Polyether polyols, and optionally in addition to water used as a reactant are used for the organic polyisocyanates.
  • the amount of the compounds according to the invention is preferably at Production of polyurethane foams chosen so that in the reaction mixture 0.01 to 1 wt .-% of tertiary nitrogen atoms of the invention Connections exist.
  • the compounds according to the invention are suitable are particularly preferred as catalysts in the production of composite bodies by back-foaming plastic films with a polyurethane foam reacting reaction mixture.
  • the compounds according to the invention can also be used for other areas of application.
  • the foams were produced using the hand foaming method. All components except the polyisocyanate component stirred for 30 s (stirring speed: 1000 rpm). Subsequently the isocyanate component is added and for 10 s at room temperature further stirred. The mixing ratio corresponds to an isocyanate index from 100.
  • the reactivity of the polyol component was determined by the start, rise, flow and setting time in parallel experiments, the polyol formulation being combined with the polyisocyanate component in a beaker with stirring at room temperature as described.
  • the start time is the time that elapses from the time the polyisocyanate is added to the start of the foaming process;
  • the rise time is the time that elapses from the time the polyisocyanate is added until the end of the foaming process;
  • the setting time is the time that elapses from the time the polyisocyanate is added until the foam is non-tacky.
  • the flow time is calculated from the difference between the rise and start times.
  • the density is the density which is calculated after cutting off the foam tip in a 660 ml beaker.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (5)

  1. Procédé de préparation d'amines tertiaires contenant des groupes carbonate et uréthane et le cas échéant des groupes hydroxy, caractérisé en ce que l'on fait réagir en un ou deux stades opératoires avec formation de carbonates et d'uréthanes
    a) un composant polyol consistant en au moins un alcool polyvalent de formule Q(OH)n et
    b) un composant amine consistant en au moins une diamine primaire-tertiaire de formule
    Figure 00200001
    avec
    c) des dérivés de l'acide carbonique choisis dans le groupe consistant en les carbonates de formule
    Figure 00200002
    l'urée, le phosgène et les esters bis-chlorocarboniques des polyols de formule (I),
    sous réserve que les proportions relatives des composants a) et b) correspondent à un rapport molaire de 4 : 1 à 16 : 1 entre les groupes hydroxy et les groupes amino primaires et que les dérivés de l'acide carbonique c) sont mis en oeuvre en quantité telle que, pour chaque mole d'amine b), on dispose de 0,5 mol du dérivé d'acide carbonique c) et qu'en outre, pour chaque mole, de groupes hydroxy du composant a), on dispose de 0,2 à 0,5 mol en plus des dérivés de l'acide carbonique c), les symboles des formules ci-dessus ayant les significations suivantes :
    Q
    représente le radical obtenu par élimination de n groupes hydroxy d'un alcool aliphatique de valence n contenant le cas échéant des groupes éthers, à un poids moléculaire dans l'intervalle de 90 à 400,
    n
    est égal à 2 ou 3,
    A
    représente un radical hydrocarboné aliphatique divalent en C2-C6, les atomes d'azote étant séparés par au moins deux atomes de carbone,
    R1 et R2,
    ayant des significations identiques ou différentes, représentent chacun un groupe alkyle en C1-C4 ou forment ensemble et avec l'atome d'azote et le cas échéant d'autres hétéroatomes un hétérocycle saturé à 5 ou 6 chaínons inerte à l'égard des dérivés de l'acide carbonique c), et
    chacun des symboles R3
    représente un groupe phényle ou alkyle en C1-C4 ou bien les deux symboles R3 représentent ensemble un groupe alkylène en C2 ou C3.
  2. Procédé selon revendication 1, caractérisé en ce que, dans un premier stade de réaction, on prépare à partir d'un composant alcool a) et d'un dérivé de l'acide carbonique c), de manière connue en soi, en maintenant un rapport de 2 : 1 à 3 : 1 entre les groupes hydroxy du composant a) et les dérivés de l'acide carbonique c), un polycarbonate contenant des groupes hydroxy qu'on fait ensuite réagir dans un deuxième stade de réaction, dans une réaction d'aminolyse, en maintenant un rapport molaire de 0,2 : 1 à 0,5 : 1 entre les groupes amino primaires et les groupes carbonate, avec les amines b), avec formation d'uréthanes.
  3. Amines tertiaires contenant des groupes carbonate et uréthane et le cas échéant des groupes hydroxy, obtenues selon les revendications 1 et 2.
  4. Utilisation des amines tertiaires obtenues selon les revendications 1 et 2 en tant que catalyseurs, éventuellement combinables chimiquement, pour la réaction d'addition des isocyanates, à la préparation de résines synthétiques de polyuréthanes par le procédé de polyaddition des isocyanates.
  5. Utilisation selon revendication 4 pour la fabrication de corps composites consistant en feuilles de résines synthétiques et mousse de polyuréthane par gonflement en mousse, à l'arrière de feuilles de résines synthétiques, d'un mélange de réaction capable de réagir avec formation d'une mousse de polyuréthane.
EP95111812A 1994-08-09 1995-07-27 Amines tertiaires ayant des groupes d'uréthane et carbonate et leur application comme catalyseurs dans la préparation des polyuréthanes Expired - Lifetime EP0696580B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4428108 1994-08-09
DE4428108A DE4428108A1 (de) 1994-08-09 1994-08-09 Carbonat- und Urethangruppen aufweisende tertiäre Amine

Publications (3)

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EP0696580A2 EP0696580A2 (fr) 1996-02-14
EP0696580A3 EP0696580A3 (fr) 1996-06-19
EP0696580B1 true EP0696580B1 (fr) 1998-01-14

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Country Status (8)

Country Link
US (1) US5705672A (fr)
EP (1) EP0696580B1 (fr)
JP (1) JP3744977B2 (fr)
KR (1) KR100375904B1 (fr)
BR (1) BR9503575A (fr)
CA (1) CA2155472C (fr)
DE (2) DE4428108A1 (fr)
ES (1) ES2111993T3 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0822933B1 (fr) * 1995-04-26 2001-10-24 Lonza AG Procede de preparation de piperidinopentanamines
US6762274B2 (en) * 2000-02-10 2004-07-13 Dow Global Technologies Inc. Low emission polyurethane polymers made with autocatalytic polyols
MXPA05013555A (es) * 2003-06-13 2006-04-05 Dow Global Technologies Inc Composicion catalizadora para obtener producto de poliuretano con buena resistencia a la hidrolisis.
CA2549846A1 (fr) * 2003-12-23 2005-07-14 Dow Global Technologies Inc. Catalyseurs non fugitifs contenant des liaisons imine et des amines tertiaires, et produits en polyurethanne obtenus a partir de ceux-ci
KR20060111599A (ko) * 2003-12-23 2006-10-27 다우 글로벌 테크놀로지스 인크. 3차 아민 캡핑된 폴리에테르 폴리올을 사용하는 폴리우레탄생성물의 자체 촉매적 제조 방법
DE102008024865A1 (de) 2008-05-23 2009-11-26 Bayer Materialscience Ag Kunststoffverbundelemente und ein Verfahren zur ihrer Herstellung
CN112011049A (zh) * 2019-05-30 2020-12-01 中国科学院化学研究所 一种热塑性聚脲弹性体及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2390551A (en) * 1943-07-10 1945-12-11 Pittsburgh Plate Glass Co Unsaturated ester-amides
US2887452A (en) * 1956-12-11 1959-05-19 Texas Co Motor lubricating oil composition
DE4030515A1 (de) * 1990-09-27 1992-04-02 Bayer Ag Neue urethane, ein verfahren zu ihrer herstellung und ihre verwendung als katalysatoren fuer das isocyanat-polyadditionsverfahren

Also Published As

Publication number Publication date
KR960007533A (ko) 1996-03-22
EP0696580A2 (fr) 1996-02-14
EP0696580A3 (fr) 1996-06-19
DE59501269D1 (de) 1998-02-19
JPH0859774A (ja) 1996-03-05
CA2155472C (fr) 2007-10-23
US5705672A (en) 1998-01-06
KR100375904B1 (ko) 2003-04-21
JP3744977B2 (ja) 2006-02-15
BR9503575A (pt) 1996-06-04
DE4428108A1 (de) 1996-02-15
ES2111993T3 (es) 1998-03-16
CA2155472A1 (fr) 1996-02-10

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